Method for producing asymmetrical 4,6-bis(aryloxy)pyrimidine derivatives

ABSTRACT

The invention relates to a novel process for preparing known asymmetrical 4,6-bis(aryloxy)pyrimidine derivatives.

The present patent application is filed under 35 U.S.C. 371 forInternational Application PCT/EPO1/02731, filed Mar. 12, 2001, which waspublished in German as International Patent Publication WO 01/72719 onOct. 4, 2001, which is entitled to the right of priority of GermanPatent Application DE 100 14 607.4, filed Mar. 24, 2000.

The invention relates to a novel process for preparing known asymmetric4,6-bis(aryloxy)pyrimidine derivatives.

Asymmetric 4,6-bis(aryloxy)pyrimidine derivatives are known and areused, for example, as pesticides in crop protection (cf. WO 94/02470, WO97/27189, WO 98/21189, WO 99/57116).

The preparation of asymmetric 4,6-bis(aryloxy)pyrimidine derivatives ismore difficult than the preparation of symmetric4,6-bis(aryloxy)pyrimidine compounds since the different aryloxy groupshave to be introduced in separate reactions.

A plurality of processes for preparing asymmetric4,6-bis(aryloxy)pyrimidine derivatives has already been disclosed.

WO 94/02470 describes the preparation of asymmetric4,6-bis(aryloxy)pyrimidine derivatives by a two-step process. Reactionof 4,6-dichloropyrimidine (A) with one equivalent of a phenol derivative(B) under basic reaction conditions and subsequent reaction with asecond phenol derivative (D) gives asymmetric 4,6-bis(aryloxy)pyrimidinederivatives (E) (cf. Scheme 1).

This process has the disadvantage that an exchange of the aryloxy groupstakes place in the second reaction step, giving a product mixture ofasymmetric 4,6-bis(aryloxy)pyrimidine derivatives (E) and the symmetric4,6-bis(aryloxy)pyrimidine derivatives (F) and (G).

As a consequence, the asymmetric 4,6-bis(aryloxy)pyrimidine derivatives(E) are obtained in poor yield and can only be isolated by complicatedseparation methods.

To avoid the problem of the exchange of the aryloxy groups to the secondreaction step, it is possible to use the starting material4,6-difluoropyrimidine (cf. Scheme 2 and WO 94/02470, EP-A1-794 177).

However, this process has the disadvantage that 4,6-difluoropyrimidinehas to be prepared by a chlorine/fluorine exchange, starting from4,6-dichloro-pyrimidine. The preparation of asymmetric4,6-bis(aryloxy)pyrimidine derivatives therefore requires an additionalreaction step. Preferred starting materials are therefore4,6-dichloropyrimidine or 4,6-dichloropyrimidine derivatives.

The preparation of asymmetric 4,6-bis(aryloxy)pyrimidine derivativesstarting from 4,6-dichloro-5-halogeno-pyrimidine analogously, to theprocess described in WO 94/02470 is described in WO 98/41513.

EP-A1-794 177, U.S. Pat. Nos. 5,849,910 and 5,977,363 describe a furtherprocess for preparing asymmetric 4,6-bis(aryloxy)pyrimidine derivatives(E) starting from 4,6-dichloropyrimidine (A) (cf. Scheme 3).

In this process, the aryloxy-chloropyrimidine derivative (C) obtainedafter the first reaction step is treated with at least one molarequivalent of a tertiary amine.

The intermediates formed are pyrimidinyl-ammonium derivatives (J), whichare reacted with phenol derivatives (D) to give asymmetrical4,6-bis(aryloxy)pyrimidine derivatives (E).

This process has the disadvantage that at least equivalent molar amountsof the tertiary amine are required, which can only be recovered usingcomplicated procedures. Moreover, the asymmetric4,6-bis(aryloxy)pyrimidine derivatives are only obtained in moderateyields. This process is therefore unsuitable for the large-scaleindustrial preparation, especially if expensive amines are used.

It has now been found that asymmetric 4,6-bis(aryloxy)pyrimidinederivatives of the general formula (I),

in which

Ar¹ represents in each case substituted or unsubstituted aryl orheterocyclyl,

X represents hydrogen, fluorine, chlorine or bromine,

L¹, L², L³, L⁴ and L⁵ are identical or different and independently ofone another each represents hydrogen, halogen, cyano, nitro,alkylcarbonyl formyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl,dialkylaminocarbonyl, in each case optionally halogen-substituted alkyl,alkoxy, alkylthio, alkylsulphinyl or alkylsulphonyl, or

L¹, L², L³ and L⁴ are identical or different and independently of oneanother each represents hydrogen, halogen, cyano, nitro, alkylcarbonyl,formyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl,dialkylaminocarbonyl, in each case optionally halogen-substituted alkyl,alkoxy, alkylthio, alkylsulphinyl or alkylsulphonyl, and

L⁵ represents one of the groups below:

where * denotes the point of attachment to the phenyl radical, and wherethe radicals

are different,

are obtained when

4,6-dichloropyrimidine derivatives of the general formula (II),

in which

X is as defined above,

a) are initially, in a first step, reacted with compounds of the generalformula (III),

Ar¹—OH,  (III)

 in which

Ar¹ is as defined above,

if appropriate in the presence of a diluent and if appropriate in thepresence of an acid acceptor,

and the resulting compounds of formula (IV),

in which

Ar¹ and X are each as defined above

are then, in a second step, reacted with compounds of the generalformula (V),

in which

L¹, L², L³, L⁴ and L⁵ are each as defined above,

if appropriate in the presence of a solvent, if appropriate in thepresence of a base and with addition of from 2 to 40 mol % of1,4-diazabicyclo[2.2.2]octane (DABCO), or

b) are initially, in a first step, reacted with compounds of the generalformula (V),

in which

L¹, L², L³, L⁴ and L⁵ are each as defined above,

if appropriate in the presence of a diluent and if appropriate in thepresence of an acid acceptor,

and the resulting compounds of the formula (VI),

in which

X, L¹, L², L³, L⁴ and L⁵ are each as defined above,

are then, in a second step, reacted with compounds of general formula(III),

Ar¹—OH,  (III)

in which

Ar¹ is as defined above,

if appropriate in the presence of a solvent, if appropriate in thepresence of a base and with addition of from 2 to 40 mol % of1,4-diazabicyclo[2.2.2]octane (DABCO).

In the definitions, the saturated or unsaturated hydrocarbon chains,such as alkyl, alkanediyl, alkenyl or alkinyl, are in each casestraight-chain or branched, including in combination with heteroatoms,such as, for example, in alkoxy, alkylthio or alkylamino. Unlessindicated otherwise, preference is given to hydrocarbon chains having 1to 6 carbon atoms. Unless indicated otherwise, hydrocarbon chains having2 to 6 carbon atoms are preferred for alkenyl or alkinyl.

Halogen generally represents fluorine, chlorine, bromine or iodine,preferably fluorine, chlorine or bromine, in particular fluorine orchlorine.

Aryl represents aromatic, mono- or polycyclic hydrocarbon rings, suchas, for example, phenyl, naphthyl, anthranyl, phenanthryl, preferablyphenyl or naphthyl, in particular phenyl.

Heterocyclyl represents saturated or unsaturated, and also aromatic,cyclic compounds where at least one ring member is a heteroatom, i.e. anatom different from carbon. If the ring contains a plurality ofheteroatoms, this can be identical or different. Preferred heteroatomsare oxygen, nitrogen or sulphur. If the ring contains a plurality ofoxygen atoms, these are adjacent. If appropriate, the cyclic compoundsform a polycyclic ring system together with other carbocyclic orheterocyclic, fused-on or bridged rings. Preference is given to mono- orbicyclic ring systems, in particular to mono- or bicyclic aromatic ringsystems.

Cycloalkyl represents saturated carbocyclic compounds which, ifappropriate, form a polycyclic ring system together with othercarbocyclic fused-on or bridged rings.

A polycyclic ring system can be attached to a heterocyclic ring or afused-on carbocyclic ring. This heterocyclyl group can also be mono- orpolysubstituted, preferably by methyl, ethyl or halogen. Preference isgiven to mono- or bicyclic ring systems, in particular mono- or bicyclicaromatic ring systems.

Halogenoalkoxy represents partially or fully halogenated alkoxy. In thecase of polyhalogenated halogenoalkoxy, the halogen atoms can beidentical or different. Preferred halogen atoms are fluorine andchlorine, in particular fluorine. If the halogenoalkoxy additionallycarries other substituents, the maximum number of halogen atoms possibleis reduced to the remaining free valencies. Unless indicated otherwise,preference is given to hydrocarbon chains having 1 to 6 carbon atoms.

Halogenoalkyl represents partially or fully halogenated alkyl. In thecase of polyhalogenated halogenoalkyl, the halogen atoms can beidentical or different. Preferred halogen atoms are fluorine andchlorine, in particular fluorine. If the halogenoalkyl additionallycarries other substituents, the maximum number of halogen atoms possibleis reduced to the remaining free valencies. Unless indicated otherwise,preference is given to hydrocarbon chains having 1 to 6 carbon atoms.

The starting materials of the formulae (III) and (V), the intermediatesof the formulae (IV) and (VI) and the end products of the generalformula (I) can be present as pure isomers of different possibleisomeric forms, for example E or Z isomers or, as appropriate, asmixtures of different possible isomeric forms, in particular ofheteroisomers, such as for example, E/Z mixtures.

In general, Ar¹ represents, in particular:

heterocyclyl having 3 to 7 ring members which is optionally substitutedby halogen or by alkyl, alkoxy, halogenoalkyl, halogenoalkoxy having ineach case 1 to 4 carbon atoms;

or represents phenyl or naphthyl, each of which is optionally mono- totetrasubstituted by identical or different substituents, the possiblesubstituents preferably being selected from the list below:

halogen, cyano, nitro, formyl, carboxyl, carbamoyl, thiocarbamoyl;

in each case straight-chain or branched alkyl, oxoalkyl, alkoxy,alkoxyalkyl, alkylthioalkyl, dialkoxyalkyl, alkylthio, alkylsulphinyl oralkylsulphonyl having in each case 1 to 8 carbon atoms;

in each case straight-chain or branched alkenyl or alkenyloxy having ineach case 2 to 6 carbon atoms;

in each case straight-chain or branched halogenoalkyl, halogenoalkoxy,halogenoalkylthio, halogenoalkylsulphinyl or halogenoalkylsulphonylhaving

in each case 1 to 6 carbon atoms and 1 to 13 identical or differenthalogen atoms;

in each case straight-chain or branched halogenoalkenyl orhalogenoalkenyloxy having in each case 2 to 6 carbon atoms and 1 to 11identical or different halogen atoms;

in each case straight-chain or branched dialkylamino;

alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkylaminocarbonyl,dialkylaminocarbonyl, arylalkylaminocarbonyl, dialkylaminocarbonyloxy,alkenylcarbonyl or alkinylcarbonyl, having 1 to 6 carbon atoms in therespective hydrocarbon chain;

cycloalkyl or cycloalkyloxy having in each case from 3 to 6 carbonatoms;

in each case doubly attached alkylene having 3 or 4 carbon atoms,oxyalkylene having 2 or 3 carbon atoms or dioxyalkylene having 1 or 2carbon atoms, each of which is optionally mono- to tetrasubstituted byidentical or different substituents from the group consisting offluorine, chlorine, oxo, methyl, trifluoromethyl and ethyl;

or a grouping

in which

A¹ represents hydrogen, hydroxyl or alkyl having 1 to 4 carbon atoms orcycloalkyl having 1 to 6 carbon atoms and

A² represents hydroxyl, methoxy, ethoxy, amino, methylamino, phenyl,benzyl or represents in each case optionally cyano-, alkoxy-,alkylthio-, alkylamino-, dialkylamino- or phenyl-substituted alkyl oralkoxy having 1 to 4 carbon atoms, or represents alkenyloxy oralkinyloxy having in each case 2 to 4 carbon atoms, and also phenyl,benzoyl, benzoylethenyl, cinnamoyl, heterocyclyl or phenylalkyl,phenylalkyloxy or heterocyclylalkyl, having in each case 1 to 3 carbonatoms in the respective alkyl moieties and being in each case optionallymono- to trisubstituted in the ring moiety by halogen and/orstraight-chain or branched alkyl or alkoxy having 1 to 4 carbon atoms.

Preference is given to compounds in which Ar¹ represents:

optionally methyl-, ethyl-, methoxy-, ethoxy-, trifluoromethyl- ortrifluoromethoxy-substituted thienyl, pyridyl or furyl;

or represents phenyl which is in each case optionally mono- totetrasubstituted by identical or different substituents, the possiblesubstituents preferably being selected from the list below:

fluorine, chlorine, bromine, iodine, cyano, nitro, formyl, carboxyl,carbamoyl, thiocarbamoyl,

methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, 1-, 2-, 3-,neo-pentyl, 1-, 2-, 3-, 4-(2-methylbutyl), 1-, 2-, 3-hexyl, 1-, 2-, 3-,4-, 5-(2-methylpentyl), 1-, 2-, 3-(3-methylpentyl), 2-ethylbutyl, 1-,3-, 4-(2,2-dimetylbutyl), 1-, 2-(2,3-dimethylbutyl), 3-oxobutyl,methoxymethyl, dimethoxymethyl,

methoxy, ethoxy, n- or i-propoxy,

methylthio, ethylthio, n- oder i-propylthio, methylsulphinyl,ethylsulphinyl, methylsulphonyl or ethylsulphonyl,

vinyl, allyl, 2-methylallyl, propene-1-yl, crotonyl, propargyl,vinyloxy, allyloxy, 2-methylallyloxy, propene-1-yloxy, crotonyloxy,propargyloxy, trifluoromethyl, trifluoroethyl,

difluoromethoxy, trifluoromethoxy, difluorochloromethoxy,trifluoroethoxy, difluoromethylthio, trifluoromethylthio,difluorochloromethylthio, trifluoromethylsulphinyl ortrifluoromethylsulphonyl, dimethylamino, diethylamino,

acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl,ethylaminocarbonyl, dimethylaminocarbonyl, diethylaminocarbonyl,dimethylaminocarbonyloxy, diethylaminocarbonyloxy, benzylaminocarbonyl,acryloyl, propioloyl, cyclopentyl, cyclohexyl,

in each case doubly attached propanediyl, ethyleneoxy, each of which isoptionally mono- to tetrasubstituted by identical or differentsubstituents from the group consisting of fluorine, chlorine, oxo,methyl and trifluoromethyl,

or a grouping

where

A¹ represents hydrogen, methyl of hydroxyl and

A² represents hydroxyl, methoxy, ethoxy, amino, methylamino, phenyl orbenzyl, and also phenyl, benzoyl, benzoylethenyl, cinnamoyl, benzyl,phenylethyl, phenylpropyl, benzyloxy,5,6-dihydro-1,4,2-dioxazin-3-ylmethyl, triazolylmethyl,benzoxazol-2-ylmethyl, 1,3-dioxan-2-yl, benzimidazol-2-yl, dioxol-2-yl,oxadiazolyl, each of which is optionally mono- to trisubstituted in thering moiety by halogen and/or straight-chain or branched alkyl or alkoxyhaving 1 to 4 carbon atoms.

In a further very particularly preferred group of compounds, Ar¹represents mono- to tetrasubstituted phenyl, where the substituents areselected from the list below:

halogen, cyano, in each case straight-chain or branched alkyl orhalogenoalkyl having in particular 1 to 4 carbon atoms.

In general, X represents, in particular, fluroine or chlorine.

Particular preference is given to compounds in which X representsfluorine.

In general, L¹, L², L³, L⁴ and L⁵ are identical or different andindependently of one another each represents in particular hydrogen,halogen, cyano, nitro, formyl, alkylcarbonyl, alkoxycarbonyl,aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl having in eachcase 1 to 6 carbon atoms, alkyl, alkoxy, alkylthio, alkylsulphinyl oralkylsulphonyl having in each case 1 to 6 carbon atoms and being in eachcase optionally substituted by 1 to 5 halogen atoms, or

L¹, L², L³ and L⁴ are identical or different and independently of oneanother each represents in particular hydrogen, halogen, cyano, nitro,formyl, alkylcarbonyl, alkoxycarbonyl, aminocarbonyl,alkylaminocarbonyl, dialkylaminocarbonyl having in each case 1 to 6carbon atoms, alkyl, alkoxy, alkylthio, alkylsulphinyl or alkylsulphonylhaving in each case 1 to 6 carbon atoms and being in each caseoptionally substituted by 1 to 5 halogen atoms and

L⁵ represents in particular one of the groups below:

where * denotes the point of attachment to the phenyl radical.

Preference is given to compounds in which L¹, L², L³ and L⁴ areidentical or different and independently of one another each preferablyrepresents hydrogen, fluorine, chlorine, bromine, cyano, nitro, acetyl,propionyl, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl,ethylaminocarbonyl, dimethylaminocarbonyl, diethylaminocarbonyl, methyl,ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- ori-propoxy, methylthio, ethylthio, methylsulphinyl, ethylsulphinyl,methylsulphonyl or ethylsulphonyl, trifluoromethyl, trifluoroethyl,difluoromethoxy, trifluoromethoxy, difluorochloromethoxy,trifluoroethoxy, difluoromethylthio, difluorochloromethylthio,trifluoromethylthio, trifluoromethylsulphinyl ortrifluoromethylsulphonyl.

In a very particularly preferred group of compounds, L¹, L², L³ and L⁴each represent hydrogen or methyl.

In a further very particularly preferred group of compounds, L¹, L², L³and L⁴ each represent hydrogen.

Preference is given to compounds in which L⁵ represents one of thegroups below:

where * denotes the point of attachment to the phenyl radical.

In a very particularly preferred group of compounds, L⁵ represents oneof the groups below:

where * denotes the point of attachment to the phenyl radical.

The abovementioned general or preferred radical definitions apply bothto the end products of the formula (I) and, correspondingly, to thestarting materials or intermediates required in each case for thepreparation.

Independently of the combination of radicals given in each case, thedefinitions of radicals given in the combinations or preferredcombinations of radicals in question specifically for these radicals canalso be replaced by any definitions of radicals of other preferredranges.

It is extremely surprising that, in the process according to theinvention, aryloxyhalogenopyrimidine derivatives react with highselectivity and yield to give asymmetric 4,6-bis(aryloxy)pyrimidinederivatives when from 2 to 40 mol % of the tertiary amine1,4-diazabicyclo[2.2.2]octane (DABCO) are added. Since it is mentionedin the prior art (cf. EP-A1-794 177, U.S. Pat. Nos. 5,849,990 and5,977,363) that this reaction requires at least a molar equivalent of atertiary amine, it is extremely surprising that this reaction can alsobe carried out with from 2 to 40 mol % of DABCO, giving excellentyields. This is confirmed by a comparative experiment in which thereaction was carried out without addition of DABCO (cf. Example 4,second step). The product can only be isolated in very poor yields.

The process according to the invention has a number of advantages. Theasymmetric 4,6-bis(aryloxy)pyrimidine derivatives are obtained in highyields and purities. Moreover, it is possible to use, as startingmaterials, 4,6-difluoropyrimidine derivatives, which are easier toobtain than 4,6-dichloropyrimidine derivatives. Traditionally, it is notnecessary to recover the amine, since only catalytic amounts of DABCOare needed for carrying out the process.

The compounds of the formula (II) required as starting materials forcarrying out the process according to the invention are known and can beprepared by known methods (cf. DE-A1-197 10 609, WO 97/49605, DE-A1-19642 533 and DE-A1-195 31299) or are commercially available products.

The compounds of the formula (III) required as starting materials forcarrying out the process according to the invention are customarycommercial products or can be prepared from the latter by simpleprocesses.

The compounds of the formula (V) required as starting materials forcarrying out the process according to the invention are known and can beprepared by known methods (cf. DE-A1 196 11 653, WO-A-95/24396, WO95/04728, WO 97/27189, WO 97/14687, WO 98/23155, WO 98/21189, WO98/55461, WO 99/09026, WO 99/57116). All other starting materials arecustomary commercial products or can be prepared from the latter bysimple processes.

Suitable diluents for carrying out the first step of the processaccording to the invention are all inert organic solvents. Theseinclude, by way of example and by way of preference, aliphatic,alicyclic or aromatic hydrocarbons, such as, for example, petroleumether, hexane, heptane, cyclohexane, methylcyclohexane, benzene,toluene, xylene or decalin; halogenated hydrocarbons, such as, forexample, chlorobenzene, dichlorobenzene, dichloromethane, chloroform,carbon tetrachloride, dichloroethane or trichloroethane; ethers, suchas, for example, diethyl ether, diisopropyl ether, methyl-t-butyl ether,methyl-t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane,1,2-diethoxyethane or anisole; ketones, such as, for example, acetone,butanone, methyl isobutyl ketone or cyclohexanone, nitriles, such as,for example, acetonitrile, propionitrile, n- or i-butyronitrile orbenzonitrile, amides, such as N,N-dimethylformamide,N,N-dimethylacetamide, N-methylformamide, N-methylpyrrolidone orhexamethylphosphoric triamide; esters, such as methyl acetate or ethylacetate; sulphoxides, such as dimethyl sulphoxide, sulphones, such assulpholane; or mixtures thereof with water. In the first step of theprocess according to the invention, preference is given to usingketones, in particular methyl isobutyl ketone.

The first step of the process according to the invention is, ifappropriate, carried out in the presence of a suitable acid acceptor.Suitable acid acceptors are all customary inorganic or organic bases.These include, by way of example and by way of preference, alkalineearth metal or alkali metal hydroxides, acetates, carbonates orbicarbonates, such as, for example, sodium hydroxide, potassiumhydroxide, sodium acetate, potassium acetate, sodium carbonate,potassium carbonate, potassium bicarbonate or sodium bicarbonate;tertiary amines, such as, for example, trimethylamine, triethylamine,tributylamine, N,N-dimethylaniline, N,N-dimethylbenzylamine, pyridine,N-methylpiperidine, N-methylmorpholine, N,N-dimethylaminopyridine,diazabicyclononene (DBN) oir diazabicycloundecene (DBU); and alsoalkaline earth metal or alkali metal hydrides, such as, for example,calcium hydride, sodium hydride or potassium hydride. In the first stepof the process according to the invention, preference is given to usingalkaline earth metal or alkalimetal carbonates, in particular potassiumcarbonate or sodium carbonate.

In the first step of the process according to the invention, thereaction temperatures can be varied within a relatively wide range. Ingeneral, the reaction is carried out at temperatures from 0° C. to 100°C., preferably at temperatures from 40° C. to 80° C.

For carrying out the process according to the invention, in general from1 to 4 mol, preferably from 1 to 1.1 mol, of the 4,6-dichloropyrimidinederivatives of the formula (II) are employed per mole of the compoundsof the formula (III).

For carrying out the process according to the invention, in general from1 to 4 mol, preferably from 1 to 1.1 mol, of the 4,6-dichloropyrimidinederivatives of the formula (II) are employed per mole of the compoundsof the formula (V).

For carrying out the first step of the process according to theinvention, the following procedure is generally adopted. The4,6-dichloropyrimidine derivative of the formula (II) is, if appropriatein the presence of a diluent, admixed with a base. The compound of theformula (III) or the compound of the formula (V) is added, ifappropriate in the presence of a diluent, and the mixture is, ifappropriate at elevated or at radius temperature, stirred until thereaction has gone to completion. After the reaction has ended, thereaction mixture is worked up in a customary manner or reacted directlyin situ in the second step of the process according to the invention.

The addition of compounds of the formula (III) or of compounds of theformula (V), if appropriate in the presence of diluent, in the firststep of the process according to the invention is carried out, inparticular, by metered addition to compounds of the formula (II)dissolved, if appropriate, in a ketone, in particular in methyl isobutylketone. The addition is carried out all at once or within a period of 12hours, preferably all at once or within a period of 6 hours.

Suitable diluents for carrying out the second step of the processaccording to the invention are all inert organic solvents. Theseinclude, by way of example and by way of preference, aliphatic,alicyclic or aromatic hydrocarbons, such as, for example, petroleumether, hexane, heptane, cyclohexane, methylcyclohexane, benzene,toluene, xylene or decalin; halogenated hydrocarbons, such as, forexample, chlorobenzene, dichlorobenzene, dichloromethane, chloroform,carbon tetrachloride, dichloroethane or trichloroethane; ethers, suchas, for example, diethyl ether, diisopropyl ether, methyl-t-butyl ether,methyl-t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane,1,2-diethoxyethane or anisole; ketones, such as, for example, acetone,butanone, methyl isobutyl ketone or cyclohexanone, nitrites, such as,for example, acetonitrile, propionitrile, n- or i-butyronitrile orbenzonitrile, amides, such as N,N-dimethylformanilide,N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone orhexamethylphosphoric triamide; esters, such as methyl acetate or ethylacetate; sulphoxides, such as dimethyl sulphoxide, sulphones, such assulpholane; or mixtures thereof with water. In the second step of theprocess according to the invention, preference is given to usingketones, in particular methyl isobutyl ketone.

The second step of the process according to the invention is, ifappropriate, carried out in the presence of a suitable acid acceptor.Suitable acid acceptors are all customary inorganic or organic bases.These include, by way of example and by way of preference, alkalineearth metal or alkali metal hydroxides, acetates, carbonates orbicarbonates, such as sodium hydroxide, potassium hydroxide, sodiumacetate, potassium acetate, sodium carbonate, potassium carbonate,potassium bicarbonate or sodium bicarbonate; and also alkaline earthmetal or alkali metal hydrides, such as, for example, calcium hydride,sodium hydride or potassium hydride. In the second step of the processaccording to the invention, preference is given to using alkaline earthmetal or alkali metal carbonates, in particular potassium carbonate orsodium carbonate.

The second step of the process according to the invention is carried outin the presence of catalytic amounts of 1,4-diazabicyclo[2.2.2]octane(DABCO).

When carrying out the second step of the process according to theinvention, the reaction temperatures can be varied within a relativelywide range. In general, the reaction is carried out at temperatures offrom 0° C. to 100° C., preferably at temperatures of from 40° C. to 90°C., in particular at temperatures of from 50° C. to 80° C.

For carrying out the process according to the invention, in general from0.8 to 4 mol, preferably from 0.95 to 1.05 mol, of the compounds of theformula (V) are employed per mole of the compounds of the formula (IV).

For carrying out the process according to the invention, in general from0.8 to 4 mol, preferably from 0.95 to 1.05 mol, of the compounds of theformula (III) are employed per mole of the compounds of the formula(VI).

For carrying out the process according to the invention, in general from2 to 40 mol %, preferably from 2 to 20 mol %, of1,4-diazabicyclo[2.2.2]octane are employed per mole of the compounds offormula (IV).

For carrying out the process according to the invention, in general from2 to 40 mol %, preferably from 2 to 20 mol %, of1,4-diazabicyclo[2.2.2]octane are employed per mole of the compounds offormula (VI).

The second step of process variant a) is generally carried out asfollows. The compounds of the formula (V) are, if appropriate in thepresence of a diluent, admixed with a base and1,4-diazabicyclo[2.2.2]octane. The compounds of the formula (IV) areadded, if appropriate in the presence of the diluent, and the mixture isstirred, if appropriate at elevated temperature. After the reaction hasended, the reaction mixture is worked up in a customary manner.

Alternatively, the second step of process variant a) can also be carriedout by admixing the compounds of the formula (IV), if appropriate in thepresence of a diluent, with a base and 1,4-diazabicyclo[2.2.2]octane.The compounds of the formula (V) are added, if appropriate in thepresence of a diluent, and the mixture is stirred, if appropriate atelevated temperature. After the reaction has ended, the reaction mixtureis worked up in a customary manner.

The second step of process variant b) is generally carried out asfollows. The compounds of the formula (III) are, if appropriate in thepresence of a diluent, admixed with a base and1,4-diazabicyclo[2.2.2]octane. The compounds of the formula (VI) areadded, if appropriate in the presence of the diluent, and the mixture isstirred, if appropriate at elevated temperature. After the reaction hasended, the reaction mixture is worked up in a customary manner.

Alternatively, process step b) can also be carried out by admixing thecompounds of the formula (VI), if appropriate in the presence of adiluent, with a base and 1,4-diazabicyclo[2.2.2]octane. The compounds ofthe formula (III) are added, if appropriate in the presence of adiluent, and the mixture is stirred, if appropriate at elevatedtemperature. After the reaction has ended, the reaction mixture isworked up in a customary manner. In a specific variant, the processaccording to the invention is carried out as a one-pot reaction.

The examples below serve to illustrate the invention. However, theinvention is not limited to the examples.

EXAMPLES Example 1

Process Variant a) or b)

4-Chloro-5-fluoro-6-[4-fluoro-3-(trifluoromethyl)phenoxy]pyrimidine

First Step

4,6-Dichloro-5-fluoropyrimidine (1.67 g, content: 98.9%) and potassiumcarbonate (1.72 g) are initially charged in methyl isobutyl ketone (5ml), and the mixture is, at 60° C., admixed dropwise over a period of 3hours with a solution of 1.8 g of 4-fluoro-3-(trifluoromethyl)phenol in5 ml of methyl isobutyl ketone. The mixture is stirred at 60° C. for 1.5hours and then cooled, admixed with water, the organic phase isseparated off, the aqueous phase is extracted once more with methylisobutyl ketone, the organic extracts are combined and dried over sodiumsulphate and the solvent is distilled off. This gives4-chloro-5-fluoro-6-[4-fluoro-3-(trifluoromethyl)phenoxy]pyrimidine(2.74 g, content: 93.9%, 83.8% of theory) as an oil.

4-[4-Chloro-3-(trifluoromethyl)phenoxy]-5-fluoro-6-[4-fluoro-3-(trifluoromethyl)phenoxy]pyrimidine

Second Step

4-Chloro-3-(trifluoromethyl)phenol (0.98 g) together with potassiumcarbonate (0.9 g) and 1,4-diazabicyclo[2.2.2]octane (DABCO) (28 mg), isinitially charged in a methyl isobutyl ketone/water mixture (8 ml, 7/1),and, at 70-80° C., admixed with a solution of4-chloro-5-fluoro-6-[4-fluoro-3-(trifluoromethyl)phenoxy]pyrimidine(1.56 g, content: 98.8%) in 7 ml of methyl isobutyl ketone. The mixtureis stirred at 70-80° C. for 2 hours and then cooled, water is added, theorganic phase is separated off, the aqueous phase is extracted withmethyl isobutyl ketone, the combined organic extracts are dried oversodium sulphate and the solvent is distilled off. This gives4-[4-chloro-3-(trifluoromethyl)phenoxy]-5-fluoro-6-[4-fluoro-3-(trifluoromethyl)phenoxy]pyrimidine(1.92 g, content: 96.5%, 79.2% of theory) as a solid.

Example 2

Process Variant a)

4-Chloro-6-(3-chloro-2-methylphenoxy)-5-fluoropyrimidine

First Step

4,6-Dichloro-5-fluoropyrimidine (16,7 g, content: 99.7%) and potassiumcarbonate (20.2 g) are initially charged in methyl isobutyl ketone (50ml), and, at 60° C., admixed dropwise over a period of 3.5 hours with asolution of 14.3 g of 3-chloro-2-methylphenol in 50 ml of methylisobutyl ketone. The mixture is stirred at 60° C. for 2 hours and thencooled, admixed with water, the organic phase is separated off, theaqueous phase is extracted once more with methyl isobutyl ketone, theorganic extracts are combined and dried over sodium sulphate and thesolvent is distilled off. This gives4-chloro-6-(3-chloro-2-methylphenoxy)-5-fluoropyrimidine (26.8 g,content: 96.7%, 95.2% of theory) as a solid.

(2E)-2-(2-{[6-(3-Chloro-2-methylphenoxy)-5-fluoro-4-pyrimidinyl]oxy}phenyl)-2-(methoxyimino)-N-methylethanamide

Second Step

(2E)-2-(2-Hydroxyphenyl)-2-(methoxyimino)-N-methylethanamide (4.16 g,content: 99.7%), together with potassium carbonate (3.7 g) and DABCO(110 mg), is initially charged in methyl isobutyl ketone (30 ml), and,at 50° C., admixed with a solution of4-chloro-6-(3-chloro-2-methylphenoxy)-5-fluoropyrimidine (5.46 g,content: 98.1%) in 30 ml of methyl isobutyl ketone. The mixture isstirred at 50° C. for 4 hours and then cooled, water is added, theorganic phase is separated off, the aqueous phase is extracted withmethyl isobutyl ketone, the combined organic extracts are dried oversodium sulphate and the solvent is distilled off. This gives(2E)-2-(2-{[6-(3-chloro-2-methylphenoxy)-5-fluoro-4-pyrimidinyl]oxy}phenyl)-2-(methoxyimino)-N-methylethanamide(9.15 g, content: 94.2%, 96.9% of theory) as an oil.

Example 3

Process Variant a)

4-Chloro-6-(2-chlorophenoxy)-5-fluoropyrimidine

First Step

4,6-Dichloro-5-fluoropyrimidine (33.5 g, content: 98.9%) and potassiumcarbonate (34.4 g) are initially charged in a methyl isobutylketone/water mixture (120 ml, 5/1) and, at 60° C., admixed dropwise overa period of 3 hours with a solution of 25.7 g of o-chlorophenol in 100ml of methyl isobutyl ketone. The mixture is stirred at 60° C. for 6hours and then cooled, the organic phase is separated off and washedwith 5% NaOH, the aqueous phase is extracted with methyl isobutylketone, the organic extracts are combined and dried over sodium sulphateand the solvent is distilled off. This gives4-chloro-6-(2-chlorophenoxy)-5-fluoropyrimidine (48.4 g, content: 95.6%,90.3% of theory) as an oil.

(E)-(2-{[6-(2-Chlorophenoxy)-5-fluoro-4-pyrimidinyl]oxy}phenyl)-(5,6-dihydro-1,4,2-dioxazin-3-yl)methanoneO-methyloxime

Second Step

(E)-5,6-Dihydro-1,4,2-dioxazin-3-yl-(2-hydroxyphenyl)methanoneO-methyloxime (11.8 g), together with potassium carbonate (9.0 g) andDABCO (280 mg), is initially charged in a methyl isobutyl ketone/watermixture (80 ml, 7/1) and, at 80° C., admixed with a solution of4-chloro-6-(2-chlorophenoxy)-5-fluoropyrimidine (13.1 g, content: 98.1%)in 70 ml of methyl isobutyl ketone. The mixture is stirred at 80° C. for1.5 hours and then cooled, water is added, the organic phase isseparated off, the aqueous phase is extracted with methyl isobutylketone, the combined organic extracts are dried over sodium sulphate andthe solvent is distilled off. This gives(E)-2-(2-{[6-(2-chlorophenoxy)-5-fluoro-4-pyrimidinyl]oxy}phenyl)-(5,6-dihydro-1,4,2-dioxazin-3-yl)methanoneO-methyloxime (23.4 g, content: 95.2%, 97.9% of theory) as a solid.

Example 4

Process Variant a)

4-Chloro-6-(2-chlorophenoxy)-5-fluoropyrimidine

First Step

4,6-Dichloro-5-fluoropyrimidine (33.5 g, content: 98.9%) and potassiumcarbonate (34.4 g) are initially charged in a methyl isobutylketone/water mixture (120 ml, 5/1), and, at 60° C., admixed dropwiseover a period of 3 hours with a solution of 25.7 g of o-chlorophenol in100 ml of methyl isobutyl ketone. The mixture is stirred at 60° C. for 6hours and then cooled, the organic phase is separated off and washedwith 5% NaOH, the aqueous phase is extracted with methyl isobutylketone, the organic extracts are combined and dried over sodium sulphateand the solvent is distilled off. This gives4-chloro-6-(2-chlorophenoxy)-5-fluoropyrimidine (48.4 g, content: 95.6%,90.3% of theory) as an oil.

(E)-(2-{[6-(2-Chlorophenoxy)-5-fluoro-4-pyrimidinyl]oxy}phenyl)-(5,6-dihydro-1,4,2-dioxazin-3-yl)methanoneO-methyloxime

Second Step, Comparative Experiment

(E)-5,6-Dihydro-1,4,2-dioxazin-3-yl-(2-hydroxyphenyl)methanoneO-methyloxime (11.8 g) and potassium carbonate (9.0 g) are initiallycharged in a methyl isobutyl ketone/water mixture (80 ml, 7/1), and, at50° C., admixed with a solution of4-chloro-6-(2-chlorophenoxy)-5-fluoropyrimidine (13.1 g, content: 98.1%)in 70 ml of methyl isobutyl ketone. The mixture is stirred at 50° C. for24 hours and then cooled, water is added, the organic phase is separatedoff, the aqueous phase is extracted with methyl isobutyl ketone, thecombined organic extracts are dried over sodium sulphate and the solventis distilled off. This gives(E)-2-(2-{[6-(2-chlorophenoxy)-5-fluoro-4-pyrimidinyl]oxy}phenyl)-(5,6-dihydro-1,4,2-dioxazin-3-yl)methanoneO-methyloxime (26.4 g, content: 33.3%, 38.6% of theory) as an oil.

Example 5

Process Variant b)

(E)-{2-[(6-Chloro-5-fluoro-4-pyrimidinyl)oxy]phenyl}(5,6-dihydro-1,4,2,-dioxazin-3-yl)methanoneO-methyloxime

First Step

4,6-Dichloro-5-fluoropyrimidine (31.8 g, content: 98.9%) and potassiumcarbonate (31.5 g) are initially charged in acetone (115 ml), and, at60° C., admixed dropwise over a period of 6 hours with a solution of44.9 g of (E)-5,6-dihydro-1,4,2-dioxazin-3-yl-(2-hydroxyphenyl)methanoneO-methyloxime in 350 ml of acetone. The mixture is stirred at 60° C. for2 hours, the acetone is distilled off, the mixture is admixed withmethylene chloride and water, the organic phase is separated off, theaqueous phase is extracted with methylene chloride, the organic extractsare combined, washed with 5% NaOH and dried over sodium sulphate and thesolvent is distilled off. This gives(E)-{2-[(6-chloro-5-fluoro-4-pyrimidinyl)oxy]phenyl}-(5,6-dihydro-1,4,2,-dioxazin-3-yl)methanoneO-methyloxime (68.0 g, content: 95.8%, 94.5% of theory) as a solid.

What is claimed is:
 1. A process for preparing a compound of formula(I):

in which Ar¹ represents substituted or unsubstituted aryl orheterocyclyl, X represents hydrogen, fluorine, chlorine, or bromine, L¹,L², L³, and L⁴ are identical or different and independently of oneanother represent hydrogen, halogen, cyano, nitro, alkylcarbonyl,formyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl,dialkylaminocarbonyl, or optionally halogen-substituted alkyl, alkoxy,alkylthio, alkylsulphinyl, or alkylsulphonyl, and L⁵ representshydrogen, halogen, cyano, nitro, alkylcarbonyl, formyl, alkoxycarbonyl,aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, or optionallyhalogen-substituted alkyl, alkoxy, alkylthio, alkylsuiphinyl, oralkylsulphonyl, or represents one of the groups:

where * denotes the point of attachment to the phenyl radical of formula(I), with the proviso that the radicals: Ar¹ and

are different from each other, comprising reacting a4,6-dichloropyrimidine derivative of formula (II):

in which X is as defined for formula (I), either (a) in a first step,with a compound of formula (III): Ar¹—OH,  (III) in which Ar¹ is asdefined for formula (I), optionally in the presence of a diluent andoptionally in the presence of an acid acceptor, to form a compound offormula (IV):

in which Ar¹ and X are each as defined for formula (I), and in a secondstep, reacting the compound of formula (IV) with a compound of formula(V):

in which L¹, L², L³, L⁴, and L⁵ are each as defined for formula (I),with addition of from 2 to 40 mol % of 1,4-diazabicyclo[2.2.2]octane,optionally in the presence of a solvent and optionally in the presenceof a base, or (b) in a first step, with a compound of formula (V):

in which L¹, L², L³, L⁴, and L⁵ are each as defined for formula (I),optionally in the presence of a diluent and optionally in the presenceof an acid acceptor, to form a compound of formula (VI):

in which X, L¹, L², L³, L⁴, and L⁵ are each as defined for formula (I),and in a second step, reacting the compound of formula (VI) with acompound of formula (III): Ar¹—OH,  (III) in which Ar¹ is as defined forformula (I), with addition of from 2 to 40 mol % of1,4-diazabicyclo[2.2.2]octane, optionally in the presence of a solventand optionally in the presence of a base.
 2. A process according toclaim 1 wherein from 2 to 20 mol % of 1,4-diazabicyclo[2.2.2]octane areused per mole of the compound of formula (IV).
 3. A process according toclaim 1 wherein from 2 to 20 mol % of 1,4-diazabicyclo[2.2.2]octane areused per mole of the compound of formula (VI).
 4. A process according toclaim 1 carried out as a one-pot process.
 5. A process according toclaim 1 wherein from 1 to 4 mol of the 4,6-dichloropyrimidine derivativeof formula (II) are employed per mole of the compound of formula (III).6. A process according to claim 1 wherein from 1 to 4 mol of the4,6-dichloropyrimidine derivative of formula (II) are employed per moleof the compound of formula (V).
 7. A process according to claim 1wherein from 0.8 to 4 mol of the compound of formula (V) are employedper mole of the compound of formula (IV).
 8. A process according toclaim 1 wherein from 0.8 to 4 mol of the compound of formula (III) areemployed per mole of the compound of formula (VI).
 9. A processaccording to claim 1 wherein Ar¹ represents: (i) heterocyclyl having 3to 7 ring members that is optionally substituted by halogen or by alkyl,alkoxy, halogenoalkyl, or halogenoalkoxy having in each case 1 to 4carbon atoms; or (ii) phenyl or naphthyl, each of which is optionallymono- to tetra-substituted by identical or different substituentsselected from the group consisting of (1) halogen, cyano, nitro, formyl,carboxyl, carbamoyl, or thiocarbamoyl; (2) straight-chain or branchedalkyl, oxoalkyl, alkoxy, alkoxyalkyl, alkylthioalkyl, dialkoxyalkyl,alkylthio, alkylsulphinyl, or alkylsulphonyl having in each case 1 to 8carbon atoms; (3) straight-chain or branched alkenyl or alkenyloxyhaving in each case 2 to 6 carbon atoms; (4) straight-chain or branchedhalogenoalkyl, halogenoalkoxy, halogenoalkylthio,halogenoalkylsulphinyl, or halogeno-alkylsulphonyl having in each case 1to 6 carbon atoms and 1 to 13 identical or different halogen atoms; (5)straight-chain or branched halogenoalkenyl or halogeno-alkenyloxy havingin each case 2 to 6 carbon atoms and 1 to 11 identical or differenthalogen atoms; (6) straight-chain or branched dialkylamino; (7)alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkylamino-carbonyl,dialkylaminocarbonyl, arylalkylaminocarbonyl, dialkylaminocarbonyloxy,alkenylcarbonyl, or alkinylcarbonyl, having 1 to 6 carbon atoms in therespective hydrocarbon chain; (8) cycloalkyl or cycloalkyloxy having ineach case from 3 to 6 carbon atoms; (9) doubly attached alkylene having3 or 4 carbon atoms, oxyalkylene having 2 or 3 carbon atoms, ordioxyalkylene having 1 or 2 carbon atoms, each of which is optionallymono- to tetrasubstituted by identical or different substituentsselected from the group consisting of fluorine, chlorine, oxo, methyl,trifluoromethyl, and ethyl; and (10) a grouping

in which: A¹ represents hydrogen, hydroxyl or alkyl having 1 to 4 carbonatoms, or cycloalkyl having 1 to 6 carbon atoms, and A² representshydroxyl, methoxy, ethoxy, amino, methylamino, phenyl, or benzyl;optionally cyano-, alkoxy-, alkylthio-, alkylamino-, dialkylamino-, orphenyl-substituted alkyl or alkoxy having 1 to 4 carbon atoms;alkenyloxy or alkinyloxy having in each case 2 to 4 carbon atoms; orphenyl, benzoyl, benzoylethenyl, cinnamoyl, heterocyclyl or phenylalkyl,phenylalkyloxy, or heterocyclylalkyl, having in each case 1 to 3 carbonatoms in the respective alkyl moieties and being in each case optionallymono- to trisubstituted in the ring moiety by halogen and/orstraight-chain or branched alkyl or alkoxy having 1 to 4 carbon atoms, Xrepresents fluorine or chlorine, L¹, L², L³, and L⁴ are identical ordifferent and independently of one another represent hydrogen, halogen,cyano, nitro, formyl; alkylcarbonyl, alkoxy-carbonyl, aminocarbonyl,alkylaminocarbonyl, dialkylaminocarbonyl having in each case 1 to 6carbon atoms; or alkyl, alkoxy, alkylthio, alkylsulphinyl, oralkylsuiphonyl having in each case 1 to 6 carbon atoms and being in eachcase optionally substituted by 1 to 5 halogen atoms, and L⁵ hydrogen,halogen, cyano, nitro, formyl; alkylcarbonyl, alkoxycarbonyl,aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl having in eachcase 1 to 6 carbon atoms; or alkyl, alkoxy, alkylthio, alkylsuiphinyl,or alkylsulphonyl having in each case 1 to 6 carbon atoms and being ineach case optionally substituted by 1 to 5 halogen atoms; or representsone of the groups:

where * denotes the point of attachment to the phenyl radical of formula(I).
 10. A process according to claim 1 wherein Ar¹ represents (i)optionally methyl-, ethyl-, methoxy-, ethoxy-, trifluoromethyl-, ortrifluoromethoxy-substituted thienyl, pyridyl, or furyl; (ii) phenylthat is optionally mono- to tetrasubstituted by identical or differentsubstituents selected from the group consisting of fluorine, chlorine,bromine, iodine, cyano, nitro, formyl, carboxyl, carbamoyl,thiocarbamoyl, methyl, ethyl, n- or i-propyl, n-, i-, s-, or t-butyl,1-, 2-, 3-, or neo-pentyl, 1-, 2-, 3-, or 4-(2-methylbutyl), 1-, 2-, or3-hexyl, 1-, 2-, 3-, 4-, or 5-(2-methylpentyl), 1-, 2-, or3-(3-methylpentyl), 2-ethylbutyl, 1-, 3-, or 4-(2,2-dimethylbutyl), 1-or 2-(2,3-dimethylbutyl), 3-oxobutyl, methoxymethyl, dimethoxymethyl,methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- ori-propylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl,ethylsulphonyl, vinyl, allyl, 2-methylallyl, propene-1-yl, crotonyl,propargyl, vinyloxy, allyloxy, 2-methylallyloxy, propene-1-yloxy,crotonyloxy, propargyloxy, trifluoromethyl, trifluoroethyl,difluoromethoxy, trifluoromethoxy, difluorochloromethoxy,trifluoroethoxy, difluoromethylthio, trifluoromethylthio,difluorochloro-methylthio, trifluoromethylsulphinyl,trifluoromethylsulphonyl, dimethylamino, diethylamino, acetyl,propionyl, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl,ethylaminocarbonyl, dimethyl-aminocarbonyl, diethylaminocarbonyl,dimethylaminocarbonyloxy, diethylaminocarbonyloxy, benzylaminocarbonyl,acryloyl, propioloyl, cyclopentyl, cyclohexyl, doubly attachedpropanediyl or ethyleneoxy, each of which is optionally mono- totetrasubstituted by identical or different substituents from the groupconsisting of fluorine, chlorine, oxo, methyl, and trifluoromethyl, anda grouping

where A¹ represents hydrogen, methyl or hydroxyl and A² representshydroxyl, methoxy, ethoxy, amino, methylamino, phenyl, or benzyl; orphenyl, benzoyl, benzoylethenyl, cinnamoyl, benzyl, phenylethyl,phenylpropyl, benzyloxy, 5,6-dihydro-1,4,2-dioxazin-3-ylmethyl,triazolylmethyl, benzoxazol-2-ylmethyl, 1,3-dioxan-2-yl,benzimidazol-2-yl, dioxol-2-yl, or oxadiazolyl, each of which isoptionally mono- to trisubstituted in the ring moiety by halogen and/orstraight-chain or branched alkyl or alkoxy having 1 to 4 carbon atoms, Xrepresents fluorine, L¹, L², L³, and L⁴ are identical or different andindependently of one another represent hydrogen, fluorine, chlorine,bromine, cyano, nitro, acetyl, propionyl, methoxycarbonyl,ethoxycarbonyl, methylaminocarbonyl, ethylaminocarbonyl,dimethylaminocarbonyl, diethylaminocarbonyl, methyl, ethyl, n- ori-propyl, n-, i-, s-, or t-butyl, methoxy, ethoxy, n- or i-propoxy,methylthio, ethylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl,ethylsulphonyl, trifluoromethyl, trifluoroethyl, difluoromethoxy,trifluoromethoxy, difluorochloro-methoxy, trifluoroethoxy,difluoromethylthio, difluorochloromethylthio, trifluoromethylthio,trifluoromethylsulphinyl, or trifluoromethylsulphonyl, and L⁵ representsone of the groups:

where * denotes the point of attachment to the phenyl radical of formula(I).
 11. A process according to claim 1 wherein Ar¹ represents: (i)optionally methyl-, ethyl-, methoxy-, ethoxy-, trifluoromethyl-, ortrifluoromethoxy-substituted thienyl, pyridyl, or furyl; or (ii) phenylthat is optionally mono- to tetrasubstituted by identical or differentsubstituents selected from the group consisting of fluorine, chlorine,bromine, iodine, cyano, nitro, formyl, carboxyl, carbamoyl,thiocarbamoyl, methyl, ethyl, n- or i-propyl, n-, i-, s-, or t-butyl,1-, 2-, 3-, or neo-pentyl, 1-, 2-, 3-, or 4-(2-methylbutyl), 1-, 2-, or3-hexyl, 1-, 2-, 3-, 4-, or 5-(2-methylpentyl), 1-, 2-, or3-(3-methylpentyl), 2-ethylbutyl, 1-, 3-, 4-(2,2-dimethylbutyl), 1- or2-(2,3-dimethylbutyl), 3-oxobutyl, methoxymethyl, dimethoxymethyl,methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- ori-propylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl,ethylsulphonyl, vinyl, allyl, 2-methylallyl, propene-1-yl, crotonyl,propargyl, vinyloxy, allyloxy, 2-methylallyloxy, propene-1-yloxy,crotonyloxy, propargyloxy, trifluoromethyl, trifluoroethyl,difluoromethoxy, trifluoromethoxy, difluorochloromethoxy,trifluoroethoxy, difluoromethylthio, trifluoromethylthio,difluorochloro-methylthio, trifluoromethylsulphinyl ortrifluoromethylsulphonyl, dimethylamino, diethylamino, acetyl,propionyl, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl,ethylaminocarbonyl, dimethylaminocarbonyl, diethylaminocarbonyl,dimethylamino-carbonyloxy, diethylaminocarbonyloxy, benzylaminocarbonyl,acryloyl, propioloyl, cyclopentyl, cyclohexyl, doubly attachedpropanediyl or ethyleneoxy, each of which is optionally mono- totetrasubstituted by identical or different substituents from the groupconsisting of fluorine, chlorine, oxo, methyl, and trifluoromethyl, anda grouping

where A¹ represents hydrogen, methyl or hydroxyl and A² representshydroxyl, methoxy, ethoxy, amino, methylamino, phenyl or benzyl; orphenyl, phenoxy, phenylthio, benzoyl, benzoylethenyl, cinnamoyl, benzyl,phenylethyl, phenylpropyl, benzyloxy, benzylthio,5,6-dihydro-1,4,2-dioxazin-3-ylmethyl, triazolylmethyl,benzoxazol-2-ylmethyl, 1,3-dioxan-2-yl, benzimidazol-2-yl, dioxol-2-yl,or oxadiazolyl, each of which is optionally mono- to trisubstituted inthe ring moiety by halogen and/or straight-chain or branched alkyl oralkoxy having 1 to 4 carbon atoms, X represents fluorine, L¹, L², L³,and L⁴ each represent hydrogen, and L⁵ represents one of the groups:

where * denotes the point of attachment to the phenyl radical of formula(I).